CN114613949B - Surface modified titanium nitride chloride electrode material and preparation method thereof - Google Patents

Surface modified titanium nitride chloride electrode material and preparation method thereof Download PDF

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CN114613949B
CN114613949B CN202210503513.9A CN202210503513A CN114613949B CN 114613949 B CN114613949 B CN 114613949B CN 202210503513 A CN202210503513 A CN 202210503513A CN 114613949 B CN114613949 B CN 114613949B
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titanium nitride
electrode material
nitride chloride
modified titanium
chloride electrode
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CN114613949A (en
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李哲东
符兵
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Zhongbo Longhui Equipment Group Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a surface modified titanium nitride chloride electrode material and a preparation method thereof, belonging to the technical field of energy and new materials. The preparation method comprises the steps of taking titanium tetrachloride and ammonia gas as raw materials, preparing titanium nitride chloride powder with a layered structure by a method of firstly combining and then heating for decomposition under the protection of non-oxygen atmosphere, and then removing chlorine on the surface of the titanium nitride chloride through a way of further heating treatment to obtain the titanium nitride chloride powder coated on the surface of titanium nitride. The preparation method provided by the invention has the advantages of cheap and easily-obtained raw materials, simple and convenient process and low cost, and is suitable for large-scale production. The invention also provides the surface modified titanium nitride chloride electrode material, and the titanium nitride layer can play a role in protecting the layered structure of the titanium nitride chloride from being stripped by the electrolyte solvent molecules of the sodium ion battery, so that the stability of the titanium nitride chloride cathode material in the repeated charging and discharging process is obviously improved.

Description

Surface modified titanium nitride chloride electrode material and preparation method thereof
Technical Field
The invention relates to the technical field of energy and new materials, in particular to a surface modified titanium nitride chloride electrode material and a preparation method thereof.
Background
Sodium-ion battery (Sodium-ion battery), a secondary battery (rechargeable battery), mainly depends on Sodium ions moving between the positive and negative electrodes to work, during charging, Na + De-intercalation from the positive electrode, intercalation into the negative electrode through the electrolyte; the reverse is true when discharging, and the working principle is similar to that of the lithium ion battery. The electrode material used by the sodium ion battery is mainly sodium salt, and compared with lithium salt, the electrode material is richer in reserve and lower in price. The sodium ion battery is very suitable for energy storage application of power grid energy storage, which has higher requirements on energy density and cost control.
One of the major obstacles to the commercial application of sodium ion batteries is the lack of excellent performance negative electrode materials. In long-term practical experience of lithium ion batteries, many layered structure materials exhibit excellent electrochemical properties. Therefore, the layered structure material is also the focus of people to search for a novel sodium ion battery cathode material.
Titanium chloronitride (TiNCl) is a layered structure material in which adjacent two Cl atoms in the structure allow intercalation of Li + 、Na + 、K + And alkali metal ions without causing significant changes in the crystal structure (j. mater. chem., 2009, 19, 2573-. This structural feature makes titanium oxynitrides meet the requirements as electrode materials for sodium ion batteries.
However, not only alkali metal ions but also small organic molecules (phys. rev. B, 2016, 86, 024516) such as tetrahydrofuran, propylene carbonate, butylene carbonate, etc. may be incorporated into the structure of titanium nitride chloride. Therefore, titanium nitride chloride has poor compatibility with an electrolyte when being directly applied as a sodium ion battery cathode material, and the layered structure of the titanium nitride chloride is peeled off due to the intercalation of electrolyte solvent molecules, which is the same mechanism as that of a graphite electrode material which is easily peeled off in an electrolyte containing propylene carbonate and causes performance degradation.
The surface coating is an effective method for solving the problem of poor compatibility of the electrode material and the electrolyte, but in the prior art, the surface coating of the electrode material is usually carried out at a high temperature (for example, the sintering temperature adopted in the electrode material surface coating method disclosed in the Chinese patent CN105977476A needs to be more than 400 ℃), and titanium nitride is easy to decompose at a temperature of more than 400 ℃, so that the titanium nitride is difficult to carry out the surface coating by adopting a conventional method.
Therefore, how to realize effective surface coating of titanium nitride chloride material is a problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a surface modified titanium nitride chloride electrode material to overcome the problem of poor compatibility of titanium nitride chloride with electrolyte when the titanium nitride chloride is directly applied as a cathode material of a sodium ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a surface modified titanium nitride chloride electrode material, which comprises the following steps:
(1) under the non-oxygen atmosphere, introducing ammonia gas into the titanium tetrachloride liquid, reacting at room temperature to 130 ℃ to obtain yellow solid, and grinding to obtain yellow powder;
(2) in a non-oxygen atmosphere, carrying out primary heat treatment on the yellow powder at 340-370 ℃ to obtain titanium nitride chloride powder;
(3) and (3) under a non-oxygen atmosphere, carrying out secondary heat treatment on the titanium nitride chloride powder at the temperature of 380-400 ℃ to obtain the surface modified titanium nitride chloride electrode material.
The preparation method provided by the invention is carried out in a non-oxygen atmosphere. Preferably, the non-oxygen atmosphere is nitrogen or an inert gas. Preferably, the inert gas is argon.
In the step (1), titanium tetrachloride and ammonia gas are subjected to a chemical combination reaction at room temperature to 130 ℃ under the protection of a non-oxygen atmosphere. After the reaction was completed, the reaction product was ground into powder.
Preferably, in the step (1), a nitrogen/ammonia mixed gas is blown into a container filled with titanium tetrachloride liquid under a nitrogen atmosphere, and the reaction is carried out until the liquid is completely converted into yellow solid, wherein the volume ratio of nitrogen to ammonia in the mixed gas is 3: 1.
Preferably, the reaction temperature is controlled to be 40-100 ℃. Further preferably, the reaction temperature is 50 to 70 ℃.
Preferably, the rotation speed of the grinding is 50-70 rpm, and the time is 0.5-2 h. More preferably, the rotation speed of the grinding is 58-62 rpm, and the time is 0.8-1 h.
In the step (2), under the protection of non-oxygen atmosphere, the compound product is heated and decomposed at 340-370 ℃, and titanium nitride chloride (TiNCl) powder with a layered structure is prepared.
Preferably, the time of the first heat treatment is 5-10 h.
Further preferably, the temperature of the first heat treatment is 345-365 ℃, and the time is 6-9 h. More preferably, the temperature of the first heat treatment is 350-360 ℃, and the time is 7-8 h.
In the step (3), the surface of the titanium nitride chloride is partially dechlorinated through a further heating heat treatment way, and titanium nitride (TiN) is generated in situ on the surface of the titanium nitride chloride and is coated on the surface of titanium nitride chloride particles.
Preferably, the time of the second heat treatment is 0.5-2 h.
More preferably, the temperature of the second heat treatment is 382 to 395 ℃ and the time is 0.6 to 1.7 hours. More preferably, the temperature of the second heat treatment is 385-390 ℃ and the time is 1-1.2 h.
The invention also provides the surface modified titanium nitride chloride electrode material prepared by the preparation method. In the surface modified titanium nitride chloride electrode material, titanium nitride is generated in situ on the surface of titanium nitride chloride and is coated on the surface of titanium nitride chloride particles to form a core-shell structure.
The invention also provides a sodium ion battery which comprises a negative electrode, a positive electrode and electrolyte, wherein the active substance of the negative electrode contains the surface modified titanium nitride chloride electrode material.
In the surface modified titanium nitride chloride electrode material, the titanium nitride layer can play a role in protecting the titanium nitride chloride layer structure from being stripped by sodium ion battery electrolyte solvent molecules, and the stability of the titanium nitride chloride cathode material in the repeated charge and discharge process is obviously improved.
Preferably, the negative electrode plate is prepared by uniformly coating the electrode slurry on an aluminum foil, transferring the aluminum foil to a vacuum oven, and drying the aluminum foil at 70 ℃ for 12 hours. The electrode slurry is obtained by mixing the surface modified titanium nitride chloride electrode material, a conductive agent and a binder.
Preferably, the electrolyte contains 1mol/L NaPF 6 EC: DEC: DMC (volume ratio 1:1:1) mixture.
The invention has the following beneficial effects:
(1) the invention provides a preparation method of a surface modified titanium nitride chloride electrode material, which takes titanium tetrachloride and ammonia gas as raw materials, prepares titanium nitride chloride powder with a layered structure by a method of firstly combining and then heating and decomposing under the protection of non-oxygen atmosphere, and partially loses chlorine on the surface of the titanium nitride chloride through a way of further heating and heat treatment to obtain the titanium nitride chloride powder coated on the surface of titanium nitride. The preparation method has the advantages of cheap and easily-obtained raw materials, simple and convenient process and low cost, and is suitable for large-scale production;
(2) according to the surface-modified titanium nitride chloride electrode material provided by the invention, the titanium nitride layer can play a role in protecting the titanium nitride chloride layered structure from being stripped by sodium ion battery electrolyte solvent molecules, and the stability of the titanium nitride chloride cathode material in the repeated charge and discharge process is obviously improved.
Drawings
FIG. 1 is an SEM photograph of a surface-modified titanium nitride chloride electrode material in example 1.
Fig. 2 is a TEM image of the surface-modified titanium chloronitride electrode material in example 1.
FIG. 3 is an SEM image of an un-surface modified titanium oxynitride material of example 1.
FIG. 4 is an XRD pattern of a surface modified titanium oxynitride material and an un-surface modified titanium oxynitride material of example 1.
FIG. 5 is a graph showing the cycle performance of the surface-modified titanium nitride oxide electrode material and the non-surface-modified titanium nitride oxide electrode material in example 1.
FIG. 6 is a graph showing the cycle performance of the surface-modified titanium nitride oxide electrode material and the non-surface-modified titanium nitride oxide electrode material in example 2.
FIG. 7 is a graph showing the cycle performance of the surface-modified titanium oxynitride electrode material and the non-surface-modified titanium oxynitride material in example 3.
Detailed Description
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.
Example 1
1. Preparation of surface modified titanium nitride chloride electrode material
(1) Blowing nitrogen/ammonia mixed gas (volume ratio is 3:1) into a container filled with titanium tetrachloride liquid under the protection of nitrogen atmosphere, controlling the temperature of the container at 55 ℃ in a water bath mode until all liquid is converted into yellow solid, and stopping introducing the gas;
(2) taking the yellow solid out of the container, and grinding the yellow solid for 1 h at the rotating speed of 60 rpm in a nitrogen atmosphere to obtain yellow powder;
(3) then placing the yellow powder in a nitrogen atmosphere furnace, and carrying out heat treatment for 8 hours at 350 ℃ to obtain titanium nitride chloride powder;
(4) and continuously heating the titanium nitride chloride powder to 385 ℃, and preserving the heat for 1.2 h to ensure that the surface of the titanium nitride chloride powder loses chlorine and is decomposed into titanium nitride, thereby obtaining the surface modified titanium nitride chloride electrode material.
2. Performance characterization
2.1 observing the surface modified titanium nitride oxide electrode material prepared in this example, fig. 1 is an SEM image of the surface modified titanium nitride oxide electrode material, fig. 2 is a TEM image of the surface modified titanium nitride oxide electrode material, and as is apparent from fig. 1 and fig. 2, a significant coating is present on the surface of the surface modified titanium nitride oxide electrode material.
When the titanium oxynitride electrode material which is not modified in the step (4) is observed, fig. 3 is an SEM image of the titanium oxynitride electrode material which is not surface-modified, and it can be seen from the SEM image that the titanium oxynitride electrode material which is not surface-modified has a smooth surface and no attachments are present.
Fig. 4 is an XRD chart of the surface-modified titanium nitride chloride electrode material and the non-surface-modified titanium nitride chloride electrode material, and the intensity of the diffraction spectrum of the surface-modified titanium nitride chloride electrode material at the position of the diffraction peak of TiN is slightly increased compared with that of the non-surface-modified titanium nitride chloride electrode material, demonstrating that the deposit generated on the surface is titanium nitride.
2.2 the surface modified titanium nitride chloride electrode material prepared in the embodiment and the non-surface modified titanium nitride chloride electrode material are subjected to performance test:
assembling the button cell: in an argon glove box, 0.425g of the obtained surface modified titanium nitride chloride electrode material or non-surface modified titanium nitride chloride electrode material is weighed, 0.05g of acetylene black serving as a conductive agent and 0.025g of LA-132 serving as a binder are added, the mixture is uniformly ground and mixed in an agate mortar to prepare electrode slurry, the electrode slurry is uniformly coated on an aluminum foil, and the electrode slurry is transferred to vacuum drying after being flakedDrying at 70 deg.C for 12 hr to obtain electrode sheet, and placing into glove box. The electrode plate is taken as a working electrode, metal sodium is taken as a counter electrode, Celgard2400 is taken as a diaphragm, and 1mol/L NaPF 6 DEC and DMC (volume ratio is 1:1:1) are taken as electrolyte and assembled to form a CR2032 button cell;
and (3) carrying out constant-current charge and discharge test on the assembled CR2032 button cell at room temperature, wherein the test voltage range is 1.0-3.0V, the charge and discharge multiplying power is 0.2C, and the cycle is 300 times.
The experimental result is shown in fig. 5, the first discharge specific capacity of the surface modified titanium nitride chloride electrode material at 0.2C is 132 mAh/g, and the specific capacity after 300 cycles is 121 mAh/g.
The first discharge specific capacity of the titanium nitride chloride electrode material which is not subjected to surface modification at 0.2 ℃ is 140 mAh/g, and the specific capacity after 300 cycles is 62 mAh/g.
It can be seen that the cycling stability of the surface modified titanium nitride chloride electrode material is obviously superior to that of the non-surface modified titanium nitride chloride electrode material.
Example 2
1. Preparation of surface modified titanium nitride chloride electrode material
(1) Blowing nitrogen/ammonia mixed gas (volume ratio is 3:1) into a container filled with titanium tetrachloride liquid under the protection of nitrogen atmosphere, controlling the temperature of the container at 55 ℃ in a water bath mode until all liquid is converted into yellow solid, and stopping introducing the gas;
(2) taking the yellow solid out of the container, and grinding the yellow solid for 0.8 h at the rotating speed of 62 rpm in a nitrogen atmosphere to obtain yellow powder;
(3) then placing the yellow powder in a nitrogen atmosphere furnace, and carrying out heat treatment for 7 h at 360 ℃ to obtain titanium nitride chloride powder;
(4) and continuously heating the titanium nitride chloride powder to 390 ℃, and preserving the heat for 1 h to ensure that the surface of the titanium nitride chloride powder loses chlorine and is decomposed into titanium nitride, thereby obtaining the surface modified titanium nitride chloride electrode material.
2. Performance characterization
The surface-modified titanium nitride chloride electrode material prepared in this example and the non-surface-modified titanium nitride chloride electrode material were subjected to performance testing:
assembling the button cell: in an argon glove box, 0.425g of the obtained surface modified titanium nitride chloride electrode material or non-surface modified titanium nitride chloride electrode material is weighed, 0.05g of acetylene black serving as a conductive agent and 0.025g of LA-132 serving as a binder are added, the mixture is uniformly ground and mixed in an agate mortar to prepare electrode slurry, the electrode slurry is uniformly coated on an aluminum foil, the electrode slurry is sliced and then transferred into a vacuum oven, the vacuum oven is dried for 12 hours at 70 ℃ to prepare an electrode slice, and the electrode slice is placed in the glove box. The electrode plate is taken as a working electrode, metal sodium is taken as a counter electrode, Celgard2400 is taken as a diaphragm, and 1mol/L NaPF 6 DEC and DMC (volume ratio is 1:1:1) are taken as electrolyte and assembled to form a CR2032 button cell;
and (3) carrying out constant-current charge and discharge test on the assembled CR2032 button cell at room temperature, wherein the test voltage range is 1.0-3.0V, the charge and discharge multiplying power is 0.2C, and the cycle is 300 times.
The experimental result is shown in fig. 6, the first discharge specific capacity of the surface modified titanium nitride chloride electrode material at 0.2C is 129 mAh/g, and the specific capacity after 300 cycles is 120 mAh/g.
The first discharge specific capacity of the titanium nitride chloride electrode material which is not subjected to surface modification at 0.2 ℃ is 132 mAh/g, and the specific capacity after 300 cycles is 61 mAh/g.
It can be seen that the cycling stability of the surface modified titanium nitride chloride electrode material is obviously superior to that of the non-surface modified titanium nitride chloride electrode material.
Example 3
1. Preparation of surface modified titanium nitride chloride electrode material
(1) Blowing nitrogen/ammonia mixed gas (volume ratio is 3:1) into a container filled with titanium tetrachloride liquid under the protection of nitrogen atmosphere, controlling the temperature of the container at 65 ℃ in a water bath mode until all liquid is converted into yellow solid, and stopping ventilation;
(2) taking the yellow solid out of the container, and grinding the yellow solid for 0.5 h at the rotating speed of 70 rpm in a nitrogen atmosphere to obtain yellow powder;
(3) then placing the yellow powder in a nitrogen atmosphere furnace, and carrying out heat treatment for 6 h at 370 ℃ to obtain titanium nitride chloride powder;
(4) and continuously heating the titanium nitride chloride powder to 395 ℃, and preserving the heat for 0.8 h to ensure that the surface of the titanium nitride chloride powder loses chlorine and is decomposed into titanium nitride, thereby obtaining the surface modified titanium nitride chloride electrode material.
2. Performance characterization
The surface-modified titanium nitride chloride electrode material prepared in this example and the non-surface-modified titanium nitride chloride electrode material were subjected to performance testing:
assembling the button cell: in an argon glove box, 0.425g of the obtained surface modified titanium nitride chloride electrode material or non-surface modified titanium nitride chloride electrode material is weighed, 0.05g of acetylene black serving as a conductive agent and 0.025g of LA-132 serving as a binder are added, the mixture is uniformly ground and mixed in an agate mortar to prepare electrode slurry, the electrode slurry is uniformly coated on an aluminum foil, the electrode slurry is sliced and then transferred into a vacuum oven, the vacuum oven is dried for 12 hours at 70 ℃ to prepare an electrode slice, and the electrode slice is placed in the glove box. The electrode plate is taken as a working electrode, metal sodium is taken as a counter electrode, Celgard2400 is taken as a diaphragm, and 1mol/L NaPF 6 DEC and DMC (volume ratio is 1:1:1) are taken as electrolyte and assembled to form a CR2032 button cell;
and (3) carrying out constant-current charge and discharge test on the assembled CR2032 button cell at room temperature, wherein the test voltage range is 1.0-3.0V, the charge and discharge multiplying power is 0.2C, and the cycle is 300 times.
The experimental result is shown in fig. 7, the first discharge specific capacity of the surface modified titanium nitride chloride electrode material at 0.2C is 124 mAh/g, and the specific capacity after 300 cycles is 111 mAh/g.
The first discharge specific capacity of the titanium nitride chloride electrode material without surface modification under 0.2C is 130 mAh/g, and the specific capacity after 300 times of circulation is 62 mAh/g.
It can be seen that the cycling stability of the surface modified titanium nitride chloride electrode material is obviously superior to that of the non-surface modified titanium nitride chloride electrode material.
From the above embodiments, the invention provides a surface-modified titanium nitride chloride electrode material, in the electrode material provided by the invention, the titanium nitride coating layer can play a role in protecting the layered structure of titanium nitride chloride from being stripped by sodium ion battery electrolyte solvent molecules, and the stability of the titanium nitride chloride cathode material in the repeated charge and discharge process is remarkably improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A preparation method of a surface modified titanium nitride chloride electrode material is characterized by comprising the following steps:
(1) under the non-oxygen atmosphere, introducing ammonia gas into the titanium tetrachloride liquid, reacting at room temperature to 130 ℃ to obtain yellow solid, and grinding to obtain yellow powder;
(2) in a non-oxygen atmosphere, carrying out primary heat treatment on the yellow powder at 340-370 ℃ to obtain titanium nitride chloride powder;
(3) and (2) under a non-oxygen atmosphere, carrying out secondary heat treatment on the titanium nitride chloride powder at 380-400 ℃ to obtain the surface modified titanium nitride chloride electrode material, wherein the surface modified titanium nitride chloride electrode material is a titanium nitride-coated titanium nitride chloride electrode material.
2. The method for producing a surface-modified titanium chloronitride electrode material according to claim 1, wherein the non-oxygen atmosphere is nitrogen or an inert gas in the steps (1) to (3).
3. The method for producing a surface-modified titanium chloronitride electrode material as claimed in claim 1, wherein in the step (1), a nitrogen/ammonia mixed gas in which the volume ratio of nitrogen to ammonia in the mixed gas is 3:1 is blown into a container containing the titanium tetrachloride liquid in a nitrogen atmosphere to react until the liquid is completely converted into a yellow solid.
4. The method for preparing the surface-modified titanium nitride chloride electrode material according to claim 1, wherein in the step (1), the reaction temperature is controlled to be 50-70 ℃.
5. The method for preparing the surface modified titanium nitride chloride electrode material according to claim 1, wherein in the step (1), the rotation speed of the grinding is 50-70 rpm, and the time is 0.5-2 h.
6. The method for preparing the surface-modified titanium nitride chloride electrode material according to claim 1, wherein the time of the first heat treatment is 5-10 hours; the time of the second heat treatment is 0.5-2 h.
7. The method for preparing the surface modified titanium nitride chloride electrode material according to claim 1, wherein in the step (2), the temperature of the first heat treatment is 350-360 ℃ and the time is 7-8 h.
8. The method for preparing the surface modified titanium nitride chloride electrode material according to claim 1, wherein in the step (3), the temperature of the second heat treatment is 385-390 ℃ and the time is 1-1.2 h.
9. A surface-modified titanium nitride chloride electrode material obtained by the production method according to any one of claims 1 to 8.
10. A sodium ion battery comprising a negative electrode, wherein the negative electrode comprises the surface modified titanium oxynitride electrode material of claim 9.
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